Monoazo dyestuffs



UnitediStates Patent 3,413,280 MONOAZO DYESTUFFS Rene de Montmollin,Riehen, and Henri Riat, Arleshcim,

Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swisscompany No Drawing. Continuation-impart of application Ser. No. 247,495,Dec. 27, 1962. This application Apr. 15, 1964, Ser. No. 360,136 Claimspriority, application Switzerland, Dec. 29, 1961, 15,175/ 61 7 Claims.(Cl. 260196) This is a continuation-in-part of our co-pendingapplication Ser, No, 247,495 filed Dec. 27, 1962, now abandoned.

The present invention provides new, valuable monoazo dyestuffs of theformula in which X represents a hydrogen atom or a sulfonic acid groupor a carboxyl group, Y represents an tat-halogenacrylamino group, Zrepresents a sulfonic acid amide group, n represents a positive integernot greater than 2 and p represents a positive integer not greater than3.

The invention provides, in particular, those dyestuffs of the formula lS0311 NH-C -lHtp-t in which Z represents a sulfonic acid amide groupalkylated and/or arylated at the nitrogen atom, one Y' represents ahydrogen atom and the other Y represents an whalogenacrylamino radical,and p represents an integer not greater than 3.

The new monoazo dyestuffs can be made by coupling diazo compoundsprepared from amines of the formula NIT:

in which X and Y have the meanings ascribed to them in Formula 1, withcoupling components of the formula Patented Nov. 26, 1968monosubstituted derivatives thereof that are substituted at the nitrogenatom in mor p-position to the sulfo group, for example, N-methyl, ethyl,propyl or isobutyl compounds.

Compounds suitable as starting products for the preparation of amines ofthe Formula 3 are those that contain an easily acylatable amino group,for example, a monoalkylamino group and also a less easily acylatableprimary amino group or a nitro group, which compounds, after theacylation, can be diazotized or reduced and diazotized. As less easilyacylatableamino groups there may be mentioned more especially those thatare in a position vicinal to an acidic group, for example, a sulfonicacid group.

Coupling components of the Formula 4 which may be used areZ-amino-8-hydroxynaphthalene-6-sulfonic acid amides or2-aminonaphthalene-6-sulfonic acid amides that couple in l-position, forexample, primary sulfonic acid amides, sulfonic acid-N-monoalkylamides,especially sulfonic acid-N-monomethylamide, sulfonic acid-N-monoethyl-amide, sulfonic acid-N-monopropylamide or sulfonicacid-N-monoisobutylamide, and identical or different sulfonicacid-N-dialkylamides that contain such alkyl radicals, sulfonicacid-N-arylamides, such as sulfonic acid-N- phenylamide or sulfonic acidN 2z6 dimethylphenylamide or advantageously, for example, sulfonicacid-N- methyl-N-phenylamide, sulfonic acid-N-,B-hydroxyethyl- Nphenylamide, sulfonic acid N methyl-N-2-carboxyphenylamide or sulfonicacid-N-morpholide; other suitable coupling components of the Formula 4which may be mentioned are the corresponding 6-sulfonic acid amides ofZ-N-methylor ethylamino-S-hydroxynaphthalene or of Z-N-methylorethylaminonaphthalene.

The diazotization of the amines serving as starting; materials in thepresent process can be carried out by methods in themselves known, forexample, with the aid 1 of mineral acids, especially hydrochloric acidand sodium nitrite, or by the methods generally used for compounds fthat are difficult to diazotize, for example, with the aid 1 ofnitrosyl-sulfuric acid. In the last-mentioned case, it is often ofadvantage to precipitate the diazo compounds,

for example, by diluting the diazotized mixture with water,

filtering and coupling in that form. The coupling is carried out in anacid medium, for example, in a medium slightly acidic to Congo Red or ina medium acidified with acetic acid. It is often of advantage toneutralize the free mineral acid that is formed during the couplingreaction, for example, with sodium acetate. Duriing the diazotization,coupling and isolation of the resulting dyestuffs, care should be takento ensure that the reactive unsaturated acylamino group remains intact.

A modification of the process of the invention consists in condensingfinished dyestuffs of the Formula 1, in which X, Z, p and n have themeanings ascribed to them in the said formula and Y represents anacylatable amino group, with suitable acylation agents, especiallychlorides 0r anhydrides of a-halogenacrylic acids as mentioned in thedescription of the amines of the Formula 3. The preparation of theaminoazo dyestuffs used as starting products in this process can beeffected by hydrolyzing the corresponding acylamino-monoazo dyestuffs orby reducing the corresponding nitromonoazo dyestuffs that are ob tainedby coupling the coupling components already mentioned with thediazotized acylamino compounds or nitranilines or with the diazotizedacylaminoor nitranilinesulfonic or carboxylic acids.

In the process of the invention, the condensation of such aminomonoazodyestuffs with the aforesaid acylation agents is carried out by methodsin themselves known, advantageously in the presence of agents capable ofbinding acid, such as sodium acetate, sodium hydroxide or sodiumcarbonate, and under conditions that ensure that the reactive radical tobe introduced remains intact, that is to say, for example, in thepresence of an organic solvent or at a relatively low to a moderatelyraised temperature in aqueous medium.

A further modification of the process of the invention consists in usingas starting materials dyestuffs of the Formula 1, in which X, Z, n and12 have the meanings ascribed to them in that formula, but in which Y,for example, represents a dihalogen-propionylamino group and producingthe dyestuffs of the invention from these dyestuffs by splitting off thehydrogen halide. The aforesaid dyestuffs to be used as startingmaterials can be prepared as described for the two first-mentionedmanufacturing processes, that is to say, by coupling or condensation.

In order to split off the hydrogen halide in accordance with the processof the invention, the aforesaid dyestuffs, that contain ana:fi-dihalogen-propionylamino group, are advantageously treated withalkali metal or alkaline earth metal hydroxide, carbonate or bicarbonateat a low to a moderately raised temperature, or with alkali metal oralkaline earth metal acetate at a raised temperature.

Likewise in the two last-mentioned manufacturing processes, care has tobe taken to ensure that the fiber-reactive radical remains intact duringthe various operations and during the subsequent isolation of thedyestulf.

The isolation of the dyestuffs obtained by the processes of theinvention is advantageously carried out at a low temperature by saltingout and filtration. If necessary, the isolated dyestuffs can be driedafter the addition of extenders or stabilizing agents; drying isadvantageously carried out at not too high a temperature and underreduced pressure. In certain cases, dry preparations can be madedirectly, that is to say, without intermediate isolation of thedyestuffs, by spray-drying the whole preparation mixture. By this methodthere are obtained new, valuable dry preparations that are suitable forthe preparation of stock solutions or dyebaths or, if desired, printingpastes.

The dyestuffs obtained by the process of the invention and themodifications thereof are new. They are valuable compounds suitable fordyeing or printing a very wide variety of materials, especiallypolyhydroxylated materials of fibrous structure, such as materials thatcontain cellulose or synthetic fibers, for example, those made ofregenerated cellulose, or natural materials, for example, cellulose,linen or more especially cotton.

The dyestuffs of the invention are specially suitable for dyeing fibrousmaterials that contain nitrogen, such as polyamides and polyurethanes,silk, leather and more especially wool, for example, from a weakly acid,neutral or weakly alkaline bath, if necessary, in the presence of theusual assistants, for example, in the presence of con- 'densationproducts of ethyleneoxide and amines of highmolecular weight. In thismanner level full dyeings are obtained on wool possessing a goodfastness to light, a good fastness to rubbing and good properties of wetfastness, e.g., fastness to milling and that also exhibit excellentevenness.

Unless otherwise stated, the parts and percentages in the followingexamples are by weight:

Example 1 hydroxide solution and acidifying the solution with 500 partsby volume of 2 N acetic acid. The whole was stirred at to C. untilcoupling was complete. 450 parts by volume of a 10 N sodium hydroxidesolution were then added to the coupling mixture, and the whole stirredfor about 3 hours at about 40 C., the 02,,8-diChlO1OP1OPlOIlYl groupbeing converted into a a-chloro-acryl group. The dyestuff suspension wasthen neutralized with about 100 parts by volume of 30% hydrochloric aciduntil it reacted weakly alkaline (pH about 8). It was then filtered, thedyestuif thoroughly washed with a 2% sodium chloride solution and driedin vacuo at to C. A red powder was obtained which dissolved in hot waterand dyed wool or polyamide fibers scarlet red tints fast to wetprocessmg.

Similar dyestuffs, that dyed wool the tints listed in Column 111 of thefollowing table from a neutral or acetic acid bath were obtained bycoupling the diazo and coupling components listed in Columns I and II inthe manner described in the above example and converting the resultingdihalogen-propionylamino dyestuffs into the correspondingot-halogen-acryl dyestuffs by elimination of hydrogen halide.

When 5-a,,B-dichloro-propionylamino-2-amino-benzenel-sulfonic acid wasused instead of 4-a, 3-dichloro-propionylamino-2-aminobenzene-l-sulfonicacid a similar dyestuff was obtained that dyed wool and polyamide fiberssomewhat more bluish red tints.

I II III Neutral 01' Diazo Component Coupling Component acetic aciddyeing on wool 1 t-afi-dibromo-pro- 2-amino-8-hydroxy- Scarlet.

pionylamino-LL naphthalene-6- aminobenzene-lsulfonic acid anilide.sulionie acid.

2 .do 2-amino-84iydr0xy- Do.

naphthalene-tisulfonic acid-N- methyl-N- benzylaniide.

3 "do .'--.nnin08-hytlro.\'y- Do.

naplitlialcne-o-sulloi1- ic acid-W16- dimethylphenylamide.

4 .do 2-amino'8-hydroxy- Do.

11a hthalene-d s tonic acid-N- ethyl-N-phcnylamide. 5 ..d0Z-aminonaphthaleno- Yellow-orange.

G-sulionie acid methyl amide.

6 5-a:B-dichloro-pro- 2-a1ninonapl1thalene- Orange.

pionyl-arniuo-B- fi-sulfonic acid-N- amino-benzeno-lmethyLN- sullonicacid. phenylainidc.

7 5-0::B-dibromo-propiu... o Do.

onyl-a1nino-2'anrin0- benzenc-l-sultonic acid.

8 ..do Q-aminoB-hydroxy- Red.

naphthalene-6- sultonic acid-N- methyl-N-phenylamide.

9 4-a,B-dibromo-prodo Scarlet.

pionylamino-2- aininobenzene-lsultonie acid.

10 do Z-amino-naphthalenc- Yellow-orange.

trsulionic acid-N- methyl-N-2- carboxy-phenylamide.

11 do 2-amino-8'hydroxy- Do.

naphthalene-6-sulionic acidN-methyl- N-2-carboxy phenylamide.

12 .do Z-amino-tkhydroxy- Rod.

napthalene-ti-sulfonie acid-N-2-carboxy-phenylanndc.

13 do 2-nmethylami.no- Orange.

naphthalenetisullonio'acid-N flhydroxy-ethyl-N- phenylanridc.

14 do humethylami- Do.

no naphthalunedisulionic-acid-N- methy1-N-2- carboxy-pheuylamide.

15 5-01 :li-dibromo' do Oran re-red.

propionylanInto-2- buiizene-l-sulfonie acid.

I II III Neutral or acetic acid dyeing on wool Diazo Component CouplingComponent Red.

DYEING PRESCRIPTION 2 parts of the dyestuif obtained as described inExample 1 were dissolved in 4000 parts of water. parts of crystallinesodium sulfate were added, and 100 parts of wellwetted wool were enteredinto the dyebath so obtained at 40 to 50 C. 2 parts of 40% acetic acidwere then added, the dyebath brought to the boil in the course of /2hour, and dyeing continued at the boil for hour. After the dyeingoperation, the wool was rinsed with cold water and dried. A scarlet reddyeing fast to washing and having a good fastness to light was obtained.

Example 2 40.2 parts of 4-a:fi-dibromopropionylamino-Z-amino-'benzene-l-sultonic acid were well stirred into a mixture of 25 parts oftit-naphthalene sulfonic acid and 500 parts of water, and the wholediazotized by the slow, dropwise addition of an aqueous solution of 6.9parts of sodium nitrite.

The diazo solution so obtained, which was free from nitrous acid, waspoured into a suspension prepared by dissolving 35.8 parts of2-amino-8-hydroxy-naphthalene- 6-su1fonic acid-N-8-hydroxyethyl-N-phenyl-amide in 200 parts by volume of an N sodiumhydroxide solution and acidifying with 200 parts by volume of 2 N aceticacid. The whole was stirred at to C. until coupling was complete. 40parts by volume of 10 N sodium hydroxide solution were then added to thecoupling mixture, and the whole stirred for about 10 minutes, theazfl-dibromopropionyl group being converted into the bromacryl group.The dyestuff suspension so-treated was then neutralized withhydrochloric acid until it reacted slightly acid (pH about 6). It wasthen filtered, the dyestuff washed with a 2% sodium chloride solutionand dried in vacuo at 80 to 90 C. A red powder was obtained thatdissolved in hot water and dyed wool or polyamide fibers yellowish redtints fast to wet processing.

When 5 -a fi-dibrorno-propionylamino-Z-aminobenzenel-sulfonic acid wasused instead of 4-ottB-dibl'0lr10-P1'O-pionyl-amino-2-aminobenzene-l-sulfonic acid, a similar dyestuff wasobtained that dyed wool and polyamide fibers somewhat more bluish redtints.

Example 3 40.2 parts of4-a:fi-dibromo-propionylamino-2-arninobenzene-l-sulfonic acid werediazotized as described in Example 2, and the diazo compound so obtainedpoured into a suspension prepared by dissolving 34.2 parts of 2N-methylamino 8-hydroxynaphthalene-6-sulfonic acid-N- methyl-N-phenylamidein 200 parts by volume of an N sodium hydroxide solution and acidifyingwith 200 parts by volume of 2 N acetic acid. The whole was stirred at 20to 25 C. until coupling was complete. 40 parts by volume of a 10 Nsodium hydroxide solution were then added to the coupling mixture, andthe whole stirred for about 10 minutes, the mfi-dibromo-propionyl groupbeing converted into the bromacryl group. The dyestuff suspension wasthen neutralized with 30% hydrochloric acid 6 until it reacted slightlyacid (pH about 6). It was then filtered, and the dyestuiI' washed with a2% sodium chloride solution and dried in vacuo at to C. A red powder wasobtained that dissolved in hot water and dyed wool or polyamide fibersbluish red tints fast to wet processlng.

When 5 -a fl-dibromopropionylamino-2-aminobenzenel-sulfonic acid wasused instead of 4-a:fl-dibromo-propionylamino 2 aminobenzene-l-suilfonicacid, a similar dyestuff was obtained that dyed wool and polyamidefibers red tints with a strong bluish cast.

Example 4 57.1 parts of the dyestuff of the formula NH, s 0 H Gang...

were neutralized in 500 parts of water with a 2 N sodium hydroxidesolution, and 16.4 parts of anhydrous sodium acetate added. A solutionof 25 parts of mfl-dibromopropionyl chloride in parts of acetone wasthen added dropwise at 0 to 5 C. in the course of 30 minutes whilestirring vigorously. After a short time the amino group was completelyacylated. To the dyestufi suspension were added 30 parts of a 10 Nsodium hydroxide solution, the whole was allowed to stand for a shorttime, and then neutralized by the addition of about 10 parts of 10 Nhydrochloric acid. The dyestuif was then precipitated by the addition ofsodium chloride, filtered and dried. The dyestuif so obtained dyed woolred tints fast to wet processing and light when applied from a neutralor acetic acid bath.

What is claimed is:

1. A monoazo dyestuif of the formula in which one Y represents ahydrogen atom and the other Y represents a member selected from thegroup consisting of an a-chloracrylaminoand an a-brornacrylamino group,n represents a positive whole number not greater than 2 and p representsa positive whole number not greater than 3, and Z represents a memberselected from the group con- 3. The monoazo dyestuff of the formula S03H bill-I2 4. The monoazo dyestuff of the formula 7. The monoazodyestuff of the formula slog; 1111-12 CH2 0 H 5 s 03H NH: 11,0:0-(1 O-NHHO 1 I (EH2 N N 5. The monoazo dyestufi of the formula 10 (3H3 S0311]:NHCHa l-IzC=CCONII SOzN 112C=C-CONH 110 S zl l@ References Cited! 6. Themonoazo dyestuff of the formula UNITED STATES PATENTS 803E NHOH: 202,931,795 4/1960 Heckendorn et al. 260-199 l FOREIGN PATENTS Q 858,1831/1961 Great Britain.

HO Br CHARLES B. PARKER, Primary Examiner.

CH; &0 D. M. PAPUGA, Assistant Examiner.

1. A MONOAZO DYESTUFF OF THE FORMULA